A heterometallic single-source molecular precursor Li2Mn2(tbaoac)(6) (1, tbaoac = tert-butyl acetoacetato) has been specifically designed to achieve the lowest decomposition temperature and a clean conversion to mixed-metal oxides. The crystal structure of this tetranuclear molecule was determined by single crystal X-ray diffraction, and the retention of heterometallic structure in solution and in the gas phase was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry, respectively. Thermal decomposition of this precursor at the temperatures as low as 310 C-o resulted in a new metastable oxide phase formulated as lithium-rich, oxygen-deficient spinel Li1.5Mn1.5O3.5. This formulation was supported by a comprehensive suite of techniques including thermogravimetric/differential thermal analysis, elemental analysis, inductively coupled mass spectrometry, iodometric titration, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy studies, and Rietveld refinement from powder X-ray diffraction data. Upon heating to about 400 C-o, this new low-temperature phase disproportionates stoichiometrically, gradually converting to layered Li2MnO3 and spinel Li1+xMn2-xO4 (x < 0.5). Further heating to 750 C-o results in formation of thermodynamically stable Li2MnO3 and LiMn2O4 phases.

Fe32+δGe35-xSix was synthesized using solid-state and chemical vapor transport reactions in both powder and single crystalline forms. Single crystal and high-resolution powder X-ray diffraction experiments revealed Fe32+δGe35-xSix to be the third member of the Fe32+δGe35-xEx (E = p-element) family of ternary compounds alongside Fe32+δGe33As2 and Fe32+δGe35-xPx. Fe32+δGe35-xSix features a two-dimensional intergrowth structure of two parent structure types: MgFe6Ge6 and Co2Al5. Similar to the other members, the stabilisation of the intergrowth structure in Fe32+δGe35-xSix occurs as a result of p-element substitution in the MgFe6Ge6-type block. The intergrowth breaks the kagome net of MgFe6Ge6 into individual hexagrams while providing additional layers of geometrically frustrated atomic arrangements. Magnetic measurements showed antiferromagnetic ordering at TN ∼ 150-160 K and spin reorientation below 80-90 K owing to the competition between magnetic interactions in the frustrated magnetic lattice of Fe32+δGe35-xSix.

A new tricationic organic supramolecular tecton has been designed and synthesized. Contrary to known mono- and dicationic species, this new molecule, being a "three-way connector", allows assembling infinite supramolecular sheets and nets upon interaction with appropriate inorganic counterpart complex anions. In this work, triprotonated 6-amino-5,7-dimethyl-1,3-diazaadamantane, comprising two secondary and one primary nitrogen atoms, is used as a trication to form hybrid compounds with iodometallate anions by forming five hydrogen bonds at a time. It is shown that the bulky cation works simultaneously as a spacer and a connector, such that the positions of inorganic [MI6]3- anions (M = Sb or Bi) in the crystal structures are defined by five hydrogen bonds and are well-separated from each other. The latter is considered as a prerequisite for the hybrid compounds to exhibit optical properties originating from the undisturbed electronic structure of individual inorganic anions.

The Δ/Λ chirality observed in octahedral molecules with chelating ligands represents the major group of "chiral-at-metal" complexes. Upon shifting from mononuclear to polynuclear systems with multiple (≥2) chiral centers, not only enantiomers but also diastereomers should be considered. We present the first, to the best of our knowledge, diastereomeric pairs Δ,Δ,Δ/Λ,Λ,Λ (1) and Δ,Δ,Λ/Λ,Λ,Δ (2) of the pentanuclear assembly [MnII(ptac)3-Na-CoIII(acac)3-Na-MnII(ptac)3] (ptac = 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate; acac = acetylacetonate). Diastereomers 1 and 2 were isolated in pure form and found to exhibit distinctly different structural characteristics. Importantly, for compounds that are applied as single-source precursors for the quaternary oxide cathode material P2-Na0.67Mn0.67Co0.33O2, the diastereomers revealed different thermal behaviors in terms of volatility and thermal stability. Unambiguous assignment of the Mn and Co positions in both diastereomers has been confirmed by the synchrotron X-ray resonant diffraction technique. Oxidation states of metal ions have been verified by the synchrotron X-ray fluorescence spectroscopy. The diastereomerization between 1 and 2 is not taking place in the solid state (crystal-to-crystal), as well as in the gas phase. The transformation between two diastereomers was observed in the solutions of noncoordinating solvents and was related to the polarities of the solvents and diastereomeric molecules.

Efficient hydrogen evolution catalysts that minimize noble metal content while maintaining high activity and durability are critically needed for scalable water electrolysis. Here, we introduce a molecular precursor strategy to synthesize intimately intermixed Rh2O3/Fe2O3 nanocomposites with precisely controlled 1 : 1 metal ratio. Thermal decomposition of heterobimetallic complex [Rh(acac)3Fe(hfac)2] (acac = acetylacetonate, hfac = hexafluoroacetylacetonate) at 300 °C yields 3D spherical Rh2O3/Fe2O3 architectures without high-temperature sintering. Electrochemical evaluation reveals that Rh2O3/Fe2O3 requires only 32 mV to reach -10 mA cm-2, dramatically lower than Rh/Rh2O3 (140 mV), commercial Rh2O3 (260 mV), or α-Fe2O3 (210 mV). The Tafel slope investigation of Rh2O3/Fe2O3 indicates a Volmer-Heyrovsky mechanism with facile proton adsorption and electron transfer, while electrochemical impedance spectroscopy shows its charge-transfer resistance is an order of magnitude lower than that of Rh/Rh2O3. Importantly, chronopotentiometry at -10 mA cm-2 reveals ultrastable performance with no observable decay over 120 hours, highlighting the exceptional long-term stability of Rh2O3/Fe2O3. Post-stability microscopy exhibits intact spherical architecture with no signs of sintering or Ostwald ripening. By integrating earth-abundant sesquioxide that promotes oxophilicity, oxygen-vacancy generation, and enhanced conductivity, the title Rh2O3/Fe2O3 catalyst uses less than half the Rh loading of Rh/Rh2O3 while delivering both superior activity and unmatched durability. This work establishes that although both individual Rh2O3 and Fe2O3 oxides exhibit poor HER activity and stability in acidic media, their intimately intermixed nanocomposite delivers dramatically enhanced performance and long-term stability. The reported mixed-oxide electrocatalyst overcomes the intrinsic limitations of single-phase oxides and provides general guiding principles for designing future high-performance mixed-oxide systems.

Re-examination of the claimed isolation and X-ray characterization of di-p-tolyl and dimesityl 1,2-disulfoxides from thermolysis of the corresponding aryl sulfinimines and thiosulfinates showed that the isolated disulfide dioxides are instead the well-known isomeric thiosulfonates, as confirmed by XAS, DART-MS, X-ray, IR and NMR methods. Concerns with the original X-ray structures are addressed. Our results agree with the DFT prediction of very weak diaryl 1,2-disulfoxide S-S bond dissociation enthalpies. For now, room-temperature-stable noncyclic 1,2-disulfoxides remain unknown.

This report describes the synthesis and characterization of two heterobimetallic Li-Zn coordination isomers [Li2Zn2(tbaoac)(6)] (tbaoac = tert-butyl acetoacetato) that have been isolated separately by the same stoichiometric reaction run in different organic solvents. The 6-coordinated zinc isomer (6-Zn) was synthesized in acetone with high yield, while the 5-coordinated one (5-Zn) was readily obtained from ethanol. The 5-Zn isomer has a low solubility in organic solvents such as alkanes and haloalkanes, while its 6-Zn counterpart exhibits a good solubility in almost all common solvents. Two isomeric molecules feature similar centrosymmetric tetranuclear cyclic assemblies, which are different in their arrangement of tbaoac ligands. While all ligands act as mu(2)-type in the structure of 5-Zn, the two tbaoac groups chelating Li appear as mu(3)-type in 6-Zn, thus providing an additional coordination for Zn ions. However, the real structural transformation between these isomers was shown to be more complex than simply making or breaking a couple of Zn-O bonds. X-ray single-crystal structure analysis, powder X-ray diffraction, multinuclear NMR, DART mass spectrometry, ICP-OES analysis, and TGA have been employed for the characterization of the isomers. The combination of powder X-ray diffraction and H-1 NMR investigation revealed that 6-Zn isomer can be quantitatively transformed to 5-Zn in ethanol, while the reverse conversion instantly takes place in acetone.

Numerous descriptions of structural isomerism in metal complexes do not list any molecular vs ionic isomers. At the same time, one of the most striking examples of structural isomerism in organic chemistry is molecular urea, which has the same atomic composition as the chemically distinct ionic ammonium cyanate. This iconic organic couple now meets its inorganic heterometallic counterpart. We introduce a new class of structural isomers, molecular vs ionic, that can be consummated in complex and coordinatively unsaturated polynuclear/heterometallic compounds. We report inorganic molecular and ionic isomers of the composition [NaCrFe (acac)3(hfac)3] (acac = acetylacetonate; hfac = hexafluoroacetylacetonate). Heterometallic molecular [CrIII(acac)3-Na-FeII(hfac)3] (1m) and ionic {[CrIII(acac)3-Na-CrIII(acac)3]+[FeII(hfac)3-Na-FeII(hfac)3]-} (1i) isomers have been isolated in pure form and characterized. While both ions are heterobimetallic trinuclear entities, the neutral counterpart is a heterotrimetallic trinuclear molecule. The two isomers exhibit distinctly different characteristics in terms of solubility, volatility, mass spectrometry ionization, and thermal behavior. Unambiguous assignment of the positions and oxidation/spin states of the Periodic Table neighbors, Fe and Cr, in both isomers have been made by a combination of characterization techniques that include synchrotron X-ray resonant diffraction, synchrotron X-ray fluorescence spectroscopy, Mössbauer spectroscopy, and DART mass spectrometry. The transformation between the two isomers that does take place in solutions of noncoordinating solvents has also been tested.

The assemblies of [M4O4] (M = metal) cubanes represent a fascinating class of materials for a variety of application fields. Although such a structural characteristic is relatively common in small molecules and in extended bulk solids, high nuclearity clusters composed of multiple [M4O4] units as their backbones are rare. In this work, we report two new Mn-oxo clusters, MnII8MnIII10O10(OOCMe)12(OMe)14(py)2 ([Mn18-Ac]) and MnII4MnIII14O14(OOCCMe3)8(OMe)14(MeOH)5(py) ([Mn18-Piv]), whose core structures are assemblies of either 6- or 7-cubanes in different packing patterns, which have been unambiguously revealed by single crystal X-ray diffraction technique. The cubane-assembled structural features can be deemed as the embryonic structures of the bulk manganese oxide. Herein, this report demonstrates the first case study of utilizing Mn-oxo clusters as precursors for the preparation of manganese oxide nanocrystals, which has never been explored before. Through a simple colloidal synthetic approach, high-quality, monodisperse Mn3O4 nanocrystals can be readily prepared by employing both precursors, while their morphologies were found to be quite different. This work confirms that the structural similarity between precursors and nanomaterials is instrumental in affording more kinetically efficient pathways for materials formation, and the structure of the precursor has a significant impact on the morphology of final nanocrystal products.

A long-standing issue about the correct identification of an important starting reagent, iron(III) hexafluoroacetylacetonate, Fe(hfac)3 (1), has been resolved. The tris-chelated mononuclear complex was found to crystallize in two polymorph modifications which can be assigned as the low-temperature (1-L) monoclinic P21/n and the high-temperature (1-H) trigonal P-3. Low-temperature polymorph 1-L was found to transform to 1-H upon sublimation at 44 °C. Two modifications are clearly distinguished by powder X-ray diffraction (PXRD), single-crystal X-ray diffraction, differential scanning calorimetry (DSC), and melting-point measurements. On the other hand, the two forms share similar characteristics in direct analysis in real-time mass spectrometry (DART-MS), attenuated total reflection (ATR) spectroscopy, and some physical properties, such as color, volatility, sensitivity, and solubility. Analysis of the literature and some of our preliminary data strongly suggest that the appearance of two polymorph modifications for trivalent metal (both transition and main group) hexafluoroacetylacetonates is a common case for several largely used complexes not yet accounted for in the crystallographic databases.

We introduce a new synthetic concept that can be broadly adopted for the low-temperature preparation of mixed-metal energy storage materials, such as phosphates, silicates, fluorides, fluorophosphates, and fluorosulfates that exhibit intrinsic low electronic conductivity and thus require a carbon modulation. The development of novel low-temperature approaches for assembling energy-related materials with a complex core-shell microstructure is of great importance for expanding their application scope. The traditional definition of single-source precursors refers to their ability to yield a phase-pure material upon thermal decomposition. We have developed a new way for the utilization of heterometallic molecular precursors in synthesis that goes beyond its common delineation as a single-phase maker. The utility of this approach has been demonstrated upon the low-temperature synthesis of lithium-iron phosphate@C, which represents a celebrated cathode material for Li-ion batteries. The first atomically precise carbonaceous molecular precursors featuring a desired Li:Fe:P ratio of 1:1:1, divalent iron, and sufficient oxygen content for the target LiFeIIPO4 phosphate were shown to enable a spontaneous formation of both the olivine core and conductive carbon shell, yielding a carbon-coated mixed-metal phosphate.

The paper describes a heterobimetallic mixed-ligand hexanuclear precursor [NaMn2(thd)4(OAc)]2 (1) (thd = 2,2,6,6-tetramethyl-3,5-heptadionate; OAc = acetate) that was designed based on its lithium homoleptic analogue, [LiMn2(thd)5], by replacing one of the thd ligands with an acetate group in order to accommodate 5-coordinated sodium instead of tetrahedral lithium ion. The complex, which is highly volatile and soluble in a variety of common solvents, has been synthesized by both the solid-state and solution methods. The unique “dimer-of-trimers” heterometallic structure consists of two trinuclear [NaMnII2(thd)4]+ units firmly bridged by two acetate ligands. X-ray diffraction techniques, DART mass spectrometry, ICP-OES analysis, and IR spectroscopy have been employed to confirm the structure and composition of the hexanuclear complex. Similar to the Li counterpart forming LiMn2O4 spinel material upon thermal decomposition, the title Na:Mn = 1:2 compound was utilized as the first single-source precursor for the low-temperature preparation of Na4Mn9O18 tunnel oxide. Importantly, four Mn sites in the hexanuclear molecule can be potentially partially substituted by other transition metals, leading to heterotri- and tetrametallic precursors for the advanced quaternary and quinary Na-ion oxide cathode materials.

An unusual heterobimetallic volatile compound [Pb2Co5(acac)14] was synthesized by the gas phase/solid-state technique. The preparation can be readily scaled up using the solution approach. X-ray powder diffraction, ICP-OES analysis, and DART mass spectrometry were engaged to confirm the composition and purity of heterobimetallic complex. The composition is unique among the large family of lead(tin): transition metal = 2:1, 1:1, and 1:2 β-diketonates compounds that are mostly represented by coordination polymers. The molecular structure of the complex was elucidated by synchrotron single crystal X-ray diffraction to reveal the unique heptanuclear moiety {Co(acac)2[Pb(acac)2-Co(acac)2-Co(acac)2]2} built upon bridging interactions of acetylacetonate oxygens to neighboring metal centers that bring their coordination numbers to six. The appearance of unique heptanuclear assembly can be attributed to the fact that the [Co(acac)2] units feature both cis- and trans-bis-bridging modes, making the polynuclear moiety rather flexible. This type of octahedral coordination is relatively unique among known lead(tin)-3d transition metal β-diketonates. Due to the high-volatility, [Pb2Co5(acac)14] can be potentially applied as a MOCVD precursor for the low-temperature preparation of lead-containing functional materials.

The amantadinium iodoacetatobismuthate(III) [C10H15NH3·(CH3)2CO]2[BiI3.67(CH3COO)1.33] is a new hybrid halometallate with iodide ions partially replaced by oxygen-containing acetates to form stronger interaction between the anionic and cationic substructures. The title compound as well-shaped orange-red crystals was synthesized by a facile reaction in acetone solution in the presence of glacial acetic acid. The crystal structure of the compound consists of the infinite anionic chains [BiI3.67(CH3COO)1.33]2– and the countercations [C10H15NH3·(CH3)2CO]+; according to the optical absorption data, the test compound is a semiconductor with a band gap of 2.06 eV.

Fe6Ge5 was synthesized from the elements both as single crystals and a polycrystalline powder. Its crystal structure was reinvestigated in a wide temperature range using high-resolution powder and single-crystal X-ray diffraction. The crystal structure of Fe6Ge5 is connected with those of other iron germanides and features an alternation of iron-rich and germanium-rich layers. The magnetic behavior was studied by magnetization measurements on a single crystal and Fe-57 Mossbauer spectroscopy. The results of both methods showed that a peculiar two-step antiferromagnetic ordering (T-N1 = 110 K, T-N2 = 330 K) takes place, with the part of iron magnetic moments remaining disordered between the transitions. Such behavior originates from the large number of both symmetrically and locally distinct iron atoms that form a weakly connected iron framework and yield the competition between ferromagnetic and antiferromagnetic in-teractions. (C) 2022 Elsevier B.V. All rights reserved.

3-Hydroxypiperidinium pentaiodide was synthesized by a facile reaction in concentrated aqueous HI. Its crystal structure comprises 3-hydroxypiperidinium cations and pentaiodide anions, the latter having geometry of cis-shaped chains composed of I-2 and I-3(-) building units. The analysis of interatomic distances, Raman spectroscopy data, and results of DFT calculations, including non-covalent interaction analysis, showed that the title compound exhibits a complex pattern of covalent and non-covalent interactions. Those include I-I covalent bonds and I...I halogen bonds within the I-5(-) anion as well as (N)H...I and (O)H...I hydrogen bonds and even weaker (C)H...I van-der-Waals interactions between the cations and anions.

A new organic-inorganic hybrid [{p-(CH3)2NH—C6H4—NH3}2Cl][BiI6] was synthesized and its crystal structure was established. The hybrid consists of an inorganic anion [BiI6]3− and an organic cation [{p-(CH3)2NH-C6H4-NH3}2Cl]3+. The [BiI6]3− anions are linked via non-covalent I...I interactions between axial atoms of neighboring anions to form chains running along the c axis of the tetragonal unit cell. In the cationic part, the Cl− anion is involved in four (N)H…Cl hydrogen bonds with hydrogen atoms of the p-(CH3)2NH—C6H4—NH32+ cation, forming a two-dimensional substructure. Alternating covalent and I...I halogen bonds in the anionic substructure and cation—anion hydrogen bonds provide the formation of a three-dimensional supramolecular structure with a band gap of 1.93 eV.

Transition metal-based endohedral cluster intermetallic compounds are interesting electron phases, which frequently exhibit superconductivity with a peculiar interplay between the critical temperature and valence electron count. We present a new Re-based endohedral gallium cluster compound, Re2Ga9Ge. Its unique crystal structure (P42/mmc space group, a = 8.0452(3) Å, c = 6.7132(2) Å) is built by two types of gallium polyhedra: monocapped Archimedean antiprisms centered by rhenium atoms and tetrahedra containing a main-group element inside. The analysis of chemical bonding shows the presence of localized pairwise interactions between the p-block elements and the formation of multicenter bonds with the participation of d-orbitals of rhenium. In the electronic band structure, the Fermi level is located in a narrow pseudogap indicating the optimum band filling and thus explaining the virtual absence of a homogeneity range. The compound exhibits Pauli paramagnetism and metallic properties with unexpectedly low thermal conductivity. A sharp anomaly observed on the magnetic susceptibility and resistivity curves presumably indicates the electronic phase transition accompanied by charge ordering at the characteristic temperature of T * = 271 K in zero magnetic field.

Despite remarkable progress in photoconversion efficiency, the toxicity of lead-based hybrid perovskites remains an important issue hindering their applications in consumer optoelectronic devices, such as solar cells, LED displays, and photodetectors. For that reason, lead-free metal halide complexes have attracted great attention as alternative optoelectronic materials. In this work, we demonstrate that reactions of two aromatic diamines with iodine in hydroiodic acid produced phenylenediammonium (PDA) and N,N-dimethyl-phenylenediammonium (DMPDA) triiodides, PDA(I3)2⋅2H2O and DMPDA(I3)I, respectively. If the source of bismuth was added, they were converted into previously reported PDA(BiI4)2⋅I2 and new (DMPDA)2(BiI6)(I3)⋅2H2O, having band gaps of 1.45 and 1.7 eV, respectively, which are in the optimal range for efficient solar light absorbers. All four compounds presented organic–inorganic hybrids, whose supramolecular structures were based on a variety of intermolecular forces, including (N)H⋅⋅⋅I and (N)H⋅⋅⋅O hydrogen bonds as well as I⋅⋅⋅I secondary and weak interactions. Details of their molecular and supramolecular structures are discussed based on single-crystal X-ray diffraction data, thermal analysis, and Raman and optical spectroscopy.